Separations, Volume 11, Issue 3 (March 2024) – 25 articles

Tofacitinib citrate (RR-isomer) is a janus kinase (JAK) inhibitor approved for the treatment of rheumatoid arthritis (RA) in adults who have had an inadequate response or intolerance to methotrexate. The presence of the enantiomer of tofacitinib citrate (SS-isomer) is monitored for quality control as a possible impurity in the final product. In this study, a reversed-phase high-performance liquid chromatography (RP-HPLC) method based on a chiral recognition mechanism for the separation of tofacitinib citrate and its enantiomer was established based on the principles of green analytical chemistry. A CHIRALPAK IH column was used with a mobile phase of ammonium acetate buffer (pH 8.0) and acetonitrile in a gradient elution at a detection wavelength of 285 nm. The calibration curve exhibited excellent linearity over the range of 0.1002–20.04 μg/mL (r = 0.9999). The average recovery of the enantiomer was 98.6% with a relative standard deviation (RSD) of 0.7%. The limit of detection (LOD) and the limit of quantitation (LOQ) were 0.04 and 0.1 μg/mL, respectively. This RP-HPLC method was suitable for detecting the enantiomers of tofacitinib citrate in tablets. Furthermore, the method proved to be environmentally friendly based on the evaluation by Analytical Eco-Scale, Analytical GREEnness (AGREE) and Green Analytical Procedure Index (GAPI). Full article

Chemical composition is a critical factor for determining the efficacy of any traditional Chinese medicine (TCM) and can be used as an indicator of commercial quality. To develop a new strategy for discovering potential quality markers (Q-markers) of TCM by integrating ultra-performance liquid chromatography-Q-extractive orbitrap/mass spectrometry (UPLC-Q-Extractive Orbitrap/MS), chemometric analysis, and network pharmacology, using Schisandra chinensis (Turcz.) Baill. (S. chinensis) as an example. The chemical profiling of S. chinensis was performed using UPLC-Q-Extractive Orbitrap/MS, followed by identification of hepatoprotective Q-markers through a comprehensive understanding of chemometric analysis and virtual target prediction of network pharmacology. Six compounds were considered potent candidates for Q-markers, which were identified as schisandrol A (6), angeloylgomisin H (10), schisantherin A (17), schisantherin B (18), schisandrin A (23), and schisandrin C (26). All Q-markers exhibited significant hepatoprotective activity, as evidenced by in vitro experiments. Subsequently, a method for simultaneous quantification was established and employed to analyse seven batches of S. chinensis. Therefore, the integrated approach of UPLC-Q-Extractive Orbitrap/MS, chemometrics, and network pharmacology proved to be an effective strategy for the discovery of Q-markers that can assist in assessing the overall chemical consistency of samples and provide a basis for quality evaluation of the material basis of S. chinensis. Full article

Xuetong, the dried stem of Kadsura heteroclita (Roxb.) Craib, is a traditional Tujia medicine extensively used to treat rheumatoid arthritis (RA). All traditional Chinese medicines (TCMs) necessitate a processing stage called “Paozhi” before clinical application. However, there is a dearth of research concerning the processing methods employed for Xuetong. To investigate the impact of vinegar and wine processing on the chemical constituents of Xuetong, this study devised a targeted offline two-dimensional (2D) high-performance liquid chromatography (HPLC) and ultra-high-performance liquid chromatography-orbitrap mass spectrometry (UHPLC-orbitrap-MS) method. By incorporating various MS data-processing techniques, such as molecular networking technology, fragment-ion similarity searching (FISh), online and offline database matching, and fragmentation pattern analysis, a total of 158 components were identified in Xuetong. Among them, 14 were verified by comparison with the reference standards. Notably, aside from triterpenoids and lignans, catechin derivatives were found to be the predominant constituents of Xuetong, and their levels exhibited a significant decrease following processing. This method significantly improved peak capacity and resolution, overcoming the limitations of 1D LC in simultaneously analyzing highly polar catechin derivatives and less polar triterpenoids and lignans. Moreover, the developed method shows promise for Xuetong’s quality control. Full article

Mg/Fe layered bimetallic oxide mulberry rod biochar composites (MFBCs) were prepared from mulberry rods and characterized using electron microscopy scanning (SEM), X-ray diffraction (XRD), Fourier infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). We investigated the adsorption properties of MFBCs for phosphorus, which was recovered via crystallization using calcium chloride as a precipitant. According to the findings, the MFBC is a layered bimetallic oxide with a specific surface area of 70.93 m²·g⁻¹. Its point of zero charge values, or pHzpc, was 7.66. The removal of phosphorus usingMFBCs gradually decreased with increasing pH, and the optimum pH for phosphorus removal was 4.0. The maximum phosphorus adsorption by MFBCs at 298 K was 29.682 mg·g⁻¹ for MFBCs. The adsorption process of phosphorus onto MFBCs is a heat absorption process, and the adsorption isothermal data of phosphorus onto MFBCs fit with the Langmuir adsorption isothermal model. Phosphorus recovery is achieved when calcium chloride is added to the phosphate-enriched desorption solution at a Ca/P molar ratio of 2.2. The phosphorus product obtained from this process is very pure hydroxyphospapatite. The recovery rate of phosphorus in the desorption solution is 99.64%. Full article

This study focused on evaluating human body odor volatiles using a chamber approach. Ten participants were asked to sit inside the chamber for 1 h, while using SPME as the extraction technique for vapor sampling. A total of 105 compounds were detected across participants, with nonanal having the highest frequency. PCA statistical analysis depicted tighter clustering in female whole-body odor profiles when compared to males, thus corroborating gender odor differences. Concurrently, various biospecimens (hand, axillary, breath) from the same participants allowed for a comparison between whole-body and individual biospecimen odor signatures. When comparing whole-body sampling and distinctive biospecimens, nonanal and decanal were the only odor volatiles shared. Statistical clustering depicted higher similarity within the odor profiles of individual biospecimens compared to odor profiles of the whole body, indicating distinctiveness of the odor chemical landscape as a function of sampling region. Overall, this study demonstrated that SPME-GC/MS methodology was successful in the extraction, detection, and identification of previously reported human scent volatiles when employing the human chamber for whole-body sampling. Our presented testing paradigm allows for a direct comparison of odor volatiles across the full body and specific body locations that allows odor markers to be furthered exploited for diagnostic and biological detection contexts. Full article

Microcystins (MCs) and nodularins (NODs) are cyanotoxins that can be found in water bodies during cyanobacterial harmful algal blooms (cyanoHABs). Consumption of water contaminated with cyanotoxins leads to health risks for humans and animals. Herein, corncob-based biochar and activated carbon (AC) were initially investigated for the sorption of six common MC congeners (MC-RR, MC-YR, MC-LR, MC-LA, MC-LW, and MC-LF) and nodularin-R (NOD-R) from spiked water. Biochar was prepared by refluxing commercial corncob with HCl and heating it to 250, 300, or 350 °C. AC was prepared by chemical activation of corncob with H₃PO₄ at 500 °C under a nitrogen atmosphere. Low-temperature nitrogen adsorption measurements confirmed that H₃PO₄-AC has a higher specific surface area (≈1100 m²/g) and total pore volume (≈0.75 cm³/g) than biochar and commercial AC. H₃PO₄-AC showed the maximum efficacy, among all corncob-based sorbents, to remove MCs and NOD-R from water as confirmed by experiments that involved sample analyses by ultrahigh-pressure liquid chromatography-mass spectrometry (UHPLC-MS). The effect of natural organic matter (NOM) on the adsorption of MCs was checked by incubating sorbents with Lake Erie water collected during cyanoHABs from 2020 to 2022. The total concentration (extracellular and intracellular) of studied MC congeners ranged from 1.37 µg/L to 438.51 µg/L and 50 mg of H₃PO₄-AC completely removed them from 3 mL of lake water. The effect of water pH on cyanotoxin adsorption was studied at pH values of 5.5, 7.0, and 8.5 at both a lower (10 μg/L each) and a higher (50 μg/L each) toxin concentration. Removal was influenced by solution pH at both concentrations when using biochar, while only at higher toxin concentration when using H₃PO₄-AC. At higher MC and NOD-R concentrations, competitive adsorption was prominent, and overall, the adsorption increased at acidic pH (5.5). The study results suggest that processed corncobs can remove a significant amount of MCs and NOD-R from water, and the measured sorption capacity of H₃PO₄-AC was ~20 mg of MC-LR and NOD-R per g of this sorbent. Full article

A sustainable reversed-phase chromatographic method has been developed and validated for the simultaneous determination of three active pharmaceutical ingredients, dorzolamide, brinzolamide, and timolol, used to treat glaucoma. The eco-friendly solvent isopropanol has been used as an organic mobile phase constituent. According to the Hansen space green solvent selection tool, isopropanol has a G score of 6.5, comparable to ethanol, which has a G score of 6.6. The mobile phase consists of isopropanol: aqueous sodium acetate buffer (0.1 M, pH 4.25) in the ratio of 10:90 (v/v). The flow rate was maintained at 1 mL/min. Dorzolamide and brinzolamide were detected at 254 nm, and timolol was detected at 295 nm. A high-purity silica with a polymeric C18 modification column (150 × 4.6 mm, 5 µm particle size) was used for this separation. The three compounds were eluted within 8 min. The method was validated according to ICH guidelines. The calibration curves were linear in the range of 20–70 µg/mL, 40–140 µg/mL, and 20–70 µg/mL for dorzolamide, brinzolamide, and timolol, respectively. The LODs were found to be 1.61 µg/mL, 1.60 µg/mL, and 3.16 µg/mL for dorzolamide, brinzolamide, and timolol, respectively. Good accuracy and precision were obtained for the three compounds. The greenness and whiteness of the method were indicated using the AGREE, ChlorTox, and RGB12 tools. Full article

Pralidoxime chloride, a highly hydrophilic antidote, cannot be effectively separated by reverse-phase high-performance liquid chromatography (RP-HPLC), unless the mobile-phase composition is varied. However, the use of ion-pairing reagents for pralidoxime separation is hindered by the persistent contamination of the stationary phase or chromatography system inside the HPLC system. Thus, this study aimed to develop a simple, rapid, and robust method based on RP-HPLC to determine pralidoxime chloride in antidote autoinjectors using a chaotropic salt as the mobile-phase additive. The use of UV detection at 270 nm allowed for the simultaneous detection of pralidoxime chloride and the internal standard, pyridine-2-aldoxime. The addition of chaotropic salts (NaPF₆, NaBF₄, and NaClO₄) and an ionic liquid ([EMIM]PF₆) increased the retention time of pralidoxime chloride. Among them, NaPF₆ exhibited the highest capacity factor in the reverse-phase C18 column. Increasing the salt concentration increased the capacity factor and the number of theoretical plates. Analytical method validation was performed to assess the linearity, accuracy, precision, recovery, and repeatability, according to the Ministry of Food and Drug Safety guidelines. Additionally, this newly developed method exhibits an adequate separation capability, making it a potential substitute for the current method employed in the United States/Korean Pharmacopoeia, and it ensures the necessary durability to maintain the robustness and reliability of the analytical system. Full article

Utilizing natural plant extracts as food additives represents a promising strategy for enhancing the quality, nutritional value, and safety of food products, benefiting both consumers and the environment. Therefore, the primary objective of this study was to develop an environmentally sustainable process for the production of solid powder derived from Allium ursinum liquid extract, with the intent of utilizing it as a natural food additive. To address the challenge of instability and enhance the solubility of bioactive compounds in A. ursinum extracts obtained through subcritical water extraction, this study employed the spray drying process. Notably, the results demonstrated the remarkable efficiency of the spray drying process, with maltodextrin as a carrier, yielding uniformly encapsulated particles with an average size of approximately 4 µm, spherical shape with smooth, intact surfaces. The most optimal conditions for achieving the highest content of total phenolics (23.10 mg GAE/g) and total flavonoids (4.92 mg CE/g) in the A. ursinum extract were identified, involving an inlet temperature of 120 °C and an 80% maltodextrin concentration. The encapsulated powders showed excellent stability, with minimal loss of total phenolics (12.64%) and total flavonoids (10.52%) after three months of storage. Physicochemical analysis confirmed the successful preservation of bioactive compounds through microencapsulation using maltodextrin, suggesting its potential for application in innovative food or pharmaceutical products. Full article

Water pollution poses a global threat to human health, particularly in terms of ensuring a safe supply of drinking water. The accumulation of heavy metals from various water sources is increasing, driving the search for effective and environmentally friendly approaches and materials for metal removal. This review investigates the selective adsorption of Pb²⁺ by humic acid (HA) in a multi-metal coexistence solution. The focus is on discussing approaches to the structural identification of HA, highlighting that separation techniques are an effective method to reduce its heterogeneity. Starting from the key structural units of HA, the study reveals the interaction between HA and heavy metals. Approaches to enhance Pb²⁺ selective adsorption are explored, proposing that introducing activating groups, Ca ion exchange, and optimizing pore structures are effective approaches for improving lead ion selective adsorption. Ca²⁺ activation is suggested as a future research direction for lead-selective adsorption. Additionally, attaining lead selective adsorption through pH regulation’s significance is emphasized. This research contributes to a fundamental understanding of HA’s role as a selective lead adsorbent while offering practical implications for developing environmentally friendly adsorbent materials. The results aim to advance knowledge in environmental science and water treatment. Full article

This study investigates lyocell-based activated carbon fibers (ACFs) for their suitability in adsorbing and electrochemically detecting toxic HCl gas. ACFs were prepared via steam activation, varying temperature (800–900 °C) and time (40–240 min) to assess their adsorption and sensing capabilities. The adjustment of activation temperature and reaction time aimed to regulate the uniformity of the pore structure and pore size of the active reaction area, as well as the number of reaction sites in the ACFs. Optimal ACFs were achieved at 900 °C for 50 min, exhibiting the highest specific surface area (1403 m²/g) and total pore volume (0.66 cm³/g). Longer reaction times resulted in pore formation and disorder, reducing mechanical strength. The ACFs prepared under optimal conditions demonstrated a rapid increase in resistance during sensor measurement, indicating a significant sensitivity to HCl gas. These findings suggest the potential of ACFs for efficient HCl gas adsorption (1626.20 mg/g) and highlight the importance of activation parameters in tailoring their properties for practical applications. Full article

Copper is a non-biodegradable heavy metal, and high levels in water bodies cause serious environmental and health issues. Douglas fir biochar has a higher number of carboxylic, phenolic, and lactonic groups, which provide suitable active sites for copper removal. Douglas fir biochar (BC) was modified using 20% solutions of KOH (KOH/BC), H₂SO₄, (H₂SO₄/BC), and Na₂CO₃ (Na₂CO₃/BC). All materials were characterized using SEM, SEM-EDS, FTIR, TGA, XRD, BET, and elemental analysis. These modifications were done to compare the activations of those sites by measuring copper removal efficiencies. KOH/BC, H₂SO₄/BC, and Na₂CO₃/BC materials gave surface areas of 389.3, 326.7, and 367.9 m² g⁻¹, respectively, compared with pristine biochar with a surface area of 578.9 m² g⁻¹. The maximum Langmuir adsorption capacities for Na₂CO₃/BC, KOH/BC, BC, and H₂SO₄/BC were 24.79, 18.31, 17.38, and 9.17 mg g⁻¹, respectively. All three modifications gave faster kinetics at 2 mg/L initial copper concentrations (pH 5) compared with pristine BC. The copper removal efficiency was demonstrated in four different spiked real water matrices. The copper removals of all four water matrices were above 90% at 2 mg/L initial concentration with a 2 g/L biochar dosage. The competitive effects of Pb²⁺, Zn²⁺, Cd²⁺, and Mg²⁺ were studied at equimolar concentrations of Cu²⁺ and competitive ions for all four materials. Full article

Nickel titanate (NiTiO₃) semiconductors and graphitic carbon nitride (g-C₃N₄) have attracted great attention as photocatalysts in the degradation of environmental pollutants because of their visible-light-driven activity. But the utilizations of both semiconductors are limited by their low specific surface area. In this study, a nano-NiTiO₃/g-C₃N₄ photocatalyst was successfully synthesized by optimizing the preparation method of photocatalyst precursors. Compared with the bulk g-C₃N₄ and bulk NiTiO₃/g-C₃N₄ composite photocatalysts, the nano-NiTiO₃/g-C₃N₄ composite catalyst displayed a larger specific surface area, a more abundant pore size structure, and superior carrier separation capabilities. According to the pseudo-first-order, the degradation rate of MB was more than 2.5–19.7 times higher than that of previous studies. The superoxide radicals (·O₂⁻) and holes (h⁺) played significant roles in the photocatalytic reaction of MB. This study provides a new idea for the synthesis of photocatalysts and the improvement in photocatalytic performance. Full article

Bat feces have been reported in traditional Chinese medicine (TCM) books to have the effect of reducing fever and improving eyesight, but the mechanism of vision improvement still needs further research. To this end, we used 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity and liquid chromatography/tandem mass spectrometry (LC/MS/MS) to analyze the antioxidant capacity of and the types of vitamins in bat feces. We hoped to screen the pharmacological components of bat feces and to explain the role that these components may play in treating visual deterioration. Our results found that bat feces had a good antioxidant capacity and mainly contained vitamins B1 (thiamine), B2 (riboflavin), B3 (nicotinamide), B3 (nicotinic acid), and B5 (pantothenic acid). Although these vitamins may help to maintain the health of the optic nerve and cornea, the vitamin content of bat feces is low, but the heavy metal content is high, as shown using inductively coupled plasma–mass spectrometry (ICP-MS) analysis. Therefore, we suggest that the use of bat feces as TCM to improve vision should be strictly restricted. Full article

A liposome vesicle is an ideal carrier for carbon nanotubes (CNTs) serving as the water channel that allows for the fast transport of water molecules, thus enhancing membrane permeability. However, a low quantity of CNTs inserted into the liposome vesicle is an important factor that limits the further improvement of the membrane flux. In the present study, a positively charged lipid, (2,3-dioleoyloxy-propyl)-trimethylammonium-chloride (DOTAP), was introduced to 1,2-dioleoyl-sn-glycero-3-phosphoethanolamineon (DOPE) liposome vesicles to tailor the vesicle charge so as to evaluate the effect of positively charged DOTAP on the insertion of CNTs into liposomes and the separation performance of thin-film nanocomposite (TFN) membranes. The results show that the addition of DOTAP increased the quantity of CNTs inserted into the liposome vesicles, as the shrinkage rate (k) and permeability (Pf) of the liposome vesicles presented an obvious increase with the increased content of DOTAP in the liposome vesicles. Moreover, it contributed to a 252.3% higher water flux for TFN membranes containing DOPE/DOTAP_2:1-CNT liposomes (the mass ratio between DOPE and DOTAP was 2:1) than thin-film composite (TFC) membranes. More importantly, it presented a 106.7% higher water flux for TFN membranes containing DOPE/DOTAP_4:1-CNT liposomes (the mass ratio between DOPE and DOTAP was 4:1), which originated from the greater number of water channels that the CNTs provided in the liposome vesicles. Overall, positively charged DOTAP effectively tailored the vesicle charge, which provided a better carrier for the insertion of a greater quantity of CNTs and contributed to the higher permeability of the TFN membranes. Full article

Cordyceps fumosorosea is a common species within the Cordyceps genus. In this study, the protective effect of Cordyceps fumosorosea mycelium was investigated to clarify the potential mechanism of alleviating acute lung injury in mice using serum metabolomic analysis, which could provide a theoretical basis for the clinical application of C. fumosorosea. Sixty mice were divided into six groups (NS, LPS, MIX, COR, COC and DMX). Lung cell nuclei were analyzed using hematoxylin and eosin staining and cellular changes were observed using transmission electron microscopy (TEM). Metabolomic analyses using liquid chromatography-mass spectrometry (LC-MS) were used to identify various compounds. In all six groups, lung nuclear inflammation was observed in the COR, COC and DMX groups, whereas the NS, LPS and MIX groups showed no cellular changes, indicating good health. Metabolomic analysis using LC-MS identified 1607 compounds across various classes. Statistical analyses, including the coefficient of variation and OPLS-DA, revealed distinct metabolic proles, indicating significant changes after the consumption of C. fumosorosea mycelia. Lipids constituted the largest proportion (30.37%) of the 30 identified classes and subclasses of metabolites. A total of 617 differentially accumulated metabolites (DAMs) were identified, both unique and shared between comparisons. Metabolite analysis identified 617 differentially accumulated metabolites, with 493 common to the LPS vs. MIX group, 75 in the LPS vs. NS group and 49 in the LPS vs. NS group and LPS vs. MIX group. This comprehensive investigation suggests that C. fumosorosea mycelia treatment holds promise as a therapeutic intervention for lung injury, influencing both the histopathological (lung) features and serum metabolic profiles. Full article

Adeno-associated viruses (AAV) are currently predominant viral transfer tools for gene therapy, and efforts are being made to design faster and more efficient methods and technologies for their manufacturing. The early selection of high-performing filters is essential for developing an ultrafiltration and diafiltration (UF/DF) process, especially when feed material is scarce, and timelines are short. However, few methods and technologies exist to enable process optimization with multiple variations in a single run. In this study, we explored the potential of Ambr^® Crossflow for high-throughput, automated screening of different membrane materials, pore sizes and different process conditions for the UF/DF step of AAV8. The best overall performance was obtained with a 100 kDa PES flat sheet cassette. The UF/DF process was further transferred to a larger scale to the Sartoflow^® Smart Tangential Flow Filtration (TFF) system using a 100 kDa PES Sartocon^® Slice 200 cassette and compared to a 100 kDa PES hollow fiber. Virus recovery, permeate flux and total protein removal values of the flat sheet cassette were similar to those achieved in small-scale devices, and higher than those of the hollow fiber, thus demonstrating similar performance at a larger process scale. The high-throughput, automated method described herein allowed to screen multiple materials and process parameters of a UF/DF process in a time- and resource-efficient way, making it a useful tool to accelerate early-stage downstream process development of AAV. Full article

Nanoporous materials offer a promising solution for gas storage applications in various scientific and engineering domains. However, several crucial challenges need to be addressed, including adsorptive capacity, rapid loading, and controlled gas delivery. A potential approach to tackle these issues is through rotation-based methods. In this study, we investigate the impact of rotation on CO₂ adsorption using activated carbon, both at the early and late stages of the adsorption process. Towards this direction, three sets of experiments were conducted: (i) adsorption isotherm with rotation at each gas loading, (ii) adsorption kinetics with multiple rotations performed in sequence 15 min after CO₂ introduction, and (iii) adsorption kinetics with a single rotation after 40 h of adsorption and repetition after another 20 h. For the first two cases, the comparison was performed by respective measurements without rotation, while for the last case, results were compared to a theoretical pseudo-first-order kinetic curve. Our findings demonstrate that rotation enhances the adsorptive capacity by an impressive 54%, accelerates kinetics by a factor of 3.25, and enables controllable gas delivery by adjusting the angular velocity. These results highlight rotation as a promising technique to optimize gas storage in nanoporous materials, facilitating advancements in numerous scientific and engineering applications. Full article

Following the trend of transport decarbonization, biodiesel has become a promising alternative fuel option. Its production includes multiple steps, all of which can be time-consuming and energy intensive. Improving any of these steps could bring considerable environmental and economic benefits. The utilization of deep eutectic solvents (DESs) for glycerol extraction from crude biodiesel has predominantly been explored as a batch process. This work provides insight into continuous column extraction. Different waste cooking oils were used to produce biodiesel via transesterification with methanol, and the selective solvent for purification was DES choline chloride–ethylene glycol (1:2.5, mol.). A laboratory Karr column at different pulsation frequencies and DES to biodiesel mass ratio was used for extraction. Plate material (steel and 3D printed PETG) and geometry influence on the efficiency of extraction were investigated. Contact angle measurement was used to measure the surface free energy of steel and PETG and the spreading ability of biodiesel and DESs on both materials. Extraction efficiency was analyzed by several analytical techniques. Higher efficiency was observed with steel plates of a triangular pitch hole arrangement. Increasing the mixing intensity and DES to biodiesel mass ratio further increased the efficiency of extraction. Full article

Microfiltration plays an increasingly important role in various fields. Consequently, elucidating the mechanism of membrane fouling has emerged as a pivotal issue that needs to be resolved. In this study, a blocking filtration model was employed to evaluate the effects of membrane properties on the fouling mechanism during the microfiltration of representative polysaccharides, namely sodium alginate, pectin, and xanthan gum. Microfiltration membranes composed of hydrophilic and hydrophobic PVDF, mixed cellulose ester, as well as hydrophilic and hydrophobic PTFE were used as filter media. The flux decline behavior was significantly affected by the membrane properties, with hydrophilic membranes exhibiting a slower decrease in filtration rate. The model analysis revealed a correlation between the blocking characteristic values and the membrane properties. Although the blocking index n showed membrane material dependence, the values of this parameter remained consistent across various filtration conditions, including the wettability of the membrane surface, solute concentration, and pressure (pectin: n = 1.86, 1.85, 1.50, and 1.50 for hydrophilic PVDF, hydrophobic PVDF, hydrophilic PTFE, and hydrophobic PTFE, respectively). The resistance coefficient k was influenced by the characteristics of the membrane surface; the k values of the hydrophobic membranes were higher than those of the hydrophilic ones (pectin: k = 0.00084, 0.00725, 0.00714, and 0.0384 s¹⁻ⁿ/cm²⁻ⁿ for hydrophilic PVDF, hydrophobic PVDF, hydrophilic PTFE, and hydrophobic PTFE, respectively). The model calculations, based on the values of n and k, demonstrated a relatively good agreement with the experimental data. Full article

Background: Recurrent approximation of retention parameters in reversed-phase HPLC is effective for revealing anomalies that are otherwise difficult to detect, namely, the reversible hydration of analytes. This was demonstrated previously for restricted sets of analytes with acetonitrile–water eluents. Expanding the number of analytes and eluents seems to be a topical problem. Two kinds of derivatives of aromatic carbonyl compounds were characterized: unsubstituted hydrazones and oximes. Methods: If analyte demonstrates no anomalies in dependences of retention times vs. concentration of organic modifier, the recurrent approximations of these dependences are linear. To explain the features of recurrent approximations, the numerical experiments were proposed and considered. The artificial shifting of one, two, or more points allows for the modeling the different kinds of deviations of approximations from linearity. Results: It was shown that hydrazones are the class of analytes having no anomalies of retention parameters. On the contrary, several anomalies were detected for oximes. Downward deviations of points in the plots of recurrent approximations of retention times are the signs of reversible hydration. This effect for methanol–water eluents was detected for the first time. Some of oximes underwent hydrolysis. Conclusions: Recurrent approximation of retention times allows detecting chemical transformations of analytes during RP HPLC analysis. Full article

Camellia oil is a high-value product with rich nutrients. Recently, the adulteration of camellia oil has become an increasingly concerning issue related to human health. In this study, electric soldering iron coupled with rapid evaporative ionization mass spectrometry (REIMS) was employed for the identification and analysis of camellia oil without any sample preparation. REIMS technology coupled with chemometrics was applied to develop an analysis model for the authentication of camellia oil adulterated with soybean oil, peanut oil, rapeseed oil, sunflower oil, and corn oil (5–40%, v/v). The results showed that different types of vegetable oils could be classified using principal component analysis-linear discriminant analysis (PCA-LDA) with a correct classification of 93.8% in leave-20%-out cross-validation and 100% correctly identified in real-time recognition. The established prediction models were found to be particularly sensitive when the camellia oil samples were adulterated with 5–40% of other oils, indicating that REIMS could be a powerful tool for the authentication and adulteration analysis of camellia oil, particularly for cases where the adulteration levels are relatively high. In conclusion, the results provide valuable insights into the potential of REIMS for the rapid, accurate, and real-time authentication and adulteration analysis of camellia oil. Full article

Lavender distillation produces huge quantities of solid waste yearly. This waste is usually discarded, resulting in serious environmental issues. However, it still contains residual essential oil and other bioactive compounds. This research reports on the development and comparison of optimized solid–liquid separation methods, i.e., microwave- (MAE) and ultrasound-assisted extraction (UAE) of phenolic compounds from lavender distillation waste. The optimal pretreatment conditions, such as waste moisture content and particle size, were also determined. The extracts were spray- or freeze-dried and the resulting powders were characterized for their physicochemical properties. The majority of the original phenolic compounds in lavender were found in the leachate fraction after distillation (61%), whereas 43% was found in the solid waste. Drying of the solid waste before extraction affected the process efficiency. UAE led to a higher phenolic content and greater antioxidant properties compared to MAE. Drying (spray or freeze) the extracts did not significantly affect their phenolic content, whereas the use of maltodextrin as a drying agent improved the drying process yield, especially when using the freeze-drying method. It is concluded that valorization of lavender distillation wastes can be achieved via an integrated process consisting of a green extraction method and a consequent drying process that results in a stable bioactive powder. Full article

Body fluid identification is fundamental in forensic science as it links a specific biological source to a genetic profile, thus providing critical clues for crime scene reconstruction. Blood is one of the most common body fluids found on the crime scene, and several strategies have been developed for its identification in recent decades. Usually, after a preliminary (or presumptive) test to determine the presence of blood (both human and non-human), a confirmatory test is needed to prove that the sample is human blood. Out of the confirmatory tests, immunochromatographic (IC) assays are the most commonly and widely used. This work gives a review of the use of commercial kits specifically developed to detect human hemoglobin or glycophorin A (a surface protein of human red cells) in forensics. Claimed sensitivity varies broadly (ranging from 0.06 to 75 nanoliters of fresh blood), but different values (as low as 0.002 nL) were found during validation procedures. Specificities are high, and the possibility of cross-reaction (with the risk of false-positive results) is so low that it can be considered negligible. False-negative results, however, can be found due to the so-called “hook effect” as well as to the target degradation/modification, which interferes with the Ag-Ab binding. In addition, the chemical compositions of the presumptive test, detergents, and washing can also promote false negative outcomes in peculiar situations. Although IC assays are rapid, inexpensive, specific, and easy to use even on the crime scene, their major limitation is represented by the destructive approach required by this kind of confirmatory test. Since the final goal of the forensic investigation is the genetic typing of a bloodstain, we will describe the strategies developed for IC assays of faint stains as well as the strategies adopted to ensure that exactly the same sample undergoes human blood identification and DNA typing. Full article

Podostroma cornu-damae, one of the lethal toxic mushrooms, is known to contain macrocyclic trichothecene mycotoxins exhibiting potent cytotoxic effects, attracting attention as an important research subject for scientists interested in natural product chemistry and toxicity research. To investigate the mycotoxins from the toxic mushroom P. cornu-damae and evaluate their cytotoxic activities, the fungus was large-cultured on solid plates and successively extracted to acquire a crude methanol (MeOH) extract. After performing successive separation and purification processes, a total of eight macrocyclic trichothecenes were isolated from the MeOH extract of plate cultures of P. cornu-damae using the liquid chromatography/mass spectrometry (LC/MS)-guided isolation technique. Extensive interpretation of nuclear magnetic resonance (NMR) spectroscopic and high-resolution (HR)-electrospray ionization (ESI)-MS data allowed for the structural identification of all isolated macrocyclic trichothecenes, including satratoxin I (1), satratoxin H (2), roridin E (3), miophytocen D (4), roridin L-2 (5), trichoverritone (6), 12′-episatratoxin H (7), and roridin F (8). We conducted a cytotoxicity evaluation of compounds 1–8 against 4T1 breast cancer cells and fibroblast cell lines (L929 cells) using the Counting Kit-8 (CCK-8) cell viability assay to validate their cytotoxic potential. Our results indicated that compounds 1–6 lack anti-cancer effects on 4T1 cells and have minimal impact on the viability of the fibroblast cell line, L929 cells. In contrast, compounds 7 and 8 exhibited no cytotoxicity in normal cells (L929) and demonstrated specific cytotoxicity in breast cancer cell lines. Notably, the cytotoxic effects of compounds 7 and 8 in 4T1 cells were significantly stronger than those observed with free doxorubicin. These findings suggest that compounds 7 and 8 may possess targeted anti-cancer effects, specifically against breast cancer cells, emphasizing their efficient and selective toxicity towards breast cancer cells. Full article